Smart laminated composite structures with piezoelectric patches are widely used in vibration control applications in several engineering fields. Precise mathematical models are required for the coupling of base structural and piezoelectric field variables. This paper presents the electro-structural analysis and optimization studies of piezoelectric energy harvester with laminated composite substrate plate subjected to base excitations. The coupled electro-mechanical equations are derived from recently proposed first-order shear deformation theory via the Hamilton’s principle by considering hygrothermal effects. The coupled-field solution is obtained from Ritz-approximation and validated with three-dimensional finite element analysis. Effects of multiple piezoelectric patch topologies over the plate surface on the open-circuit voltage and displacement response are illustrated. Furthermore, the influences of piezoelectric-patch sizes, ply-orientation, size, and location of the tip mass are initially studied on the magnitude of output power and efficiency. An optimization study is conducted to identify the geometric and material variables for improvement of the harvester power output and efficiency.